Barrier film

ABSTRACT

Provided is a barrier film, comprising a base layer and an inorganic layer including a first region and a second region, which have different elemental contents (atomic %) of Si, N, and O from each other as measured by XPS, and having a compactness expressed through an etching rate of 0.17 nm/s in the thickness direction for an Ar ion etching condition to etch Ta 2 O 5  at a rate of 0.09 nm/s, wherein the second region has a higher elemental content of N than that of the first region, and the second region has a thickness of 10% or more relative to the total thickness of the inorganic layer. The barrier film has excellent barrier properties and optical properties and can be used for electronic products which are sensitive to moisture and the like.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a National Stage Application of InternationalApplication No. PCT/KR2019/013861 filed on Oct. 22, 2019, which claimspriority to and the benefit of Korean Patent Application No.10-2018-0128798 filed on Oct. 26, 2018, the disclosure of which isincorporated herein by reference in its entirety.

TECHNICAL FIELD

The present application relates to a barrier film. In particular, thepresent application relates to a barrier film having excellent barrierproperties against foreign substances such as oxygen or moisture.

BACKGROUND

Barrier films for blocking external components such as oxygen andmoisture are used not only for packaging materials of foods ormedicines, and the like which are conventional main applications, butalso members for FPDs (flat panel displays) such as LCDs (liquid crystaldisplays) or solar cells, substrates for electronic papers or OLEDs(organic light emitting diodes) or sealing films, and the like. Inparticular, in the case of barrier films used in electrical orelectronic elements, resistance to moist heat that barrier properties donot deteriorate even after being left in moist-heat conditions from theviewpoint of ensuring the performance of the apparatuses is alsorequired, in addition to high barrier properties against oxygen ormoisture, and the like.

The method for producing a barrier film can include, for example, a wetmethod. Specifically, the barrier film can be produced through a methodof converting polysilazane coated on a base film into silica. At thistime, the polysilazane can be converted to silica while undergoing aprocess such as heating under a predetermined condition or hydrolysis.For example, Japanese Patent Laid-Open Publication No. H10-194873discloses a method of applying perhydropolysilazane or its modifiedproduct to a base film and firing it under vacuum.

DISCLOSURE Technical Problem

It is one object of the present application to provide a barrier filmhaving excellent barrier properties against foreign substances such asoxygen or moisture.

It is another object of the present application to provide a packagingmaterial, apparatus or device comprising the barrier film.

The above objects of the present application and other objects can allbe solved by the present application described in detail below.

Technical Solution

In one example of the present application, the present applicationrelates to a barrier film. In the present application, the barrier filmmeans a film that satisfies the intended light transmittance and barrierproperties.

With regard to light transmittance, the barrier film can mean a filmhaving transmittance of 90% or more, or 95% or more for visible light ina wavelength range of 380 to 780 nm, specifically, light having awavelength of 550 nm. The upper limit of the transmittance is, forexample, about 100%, where the film can have transmittance of less than100%.

With regard to the barrier properties, the barrier film can have a goodwater vapor transmission rate.

In one example, the barrier film can satisfy a water vapor transmissionrate of 10×10⁻⁴ g/m²·day or less as measured at a temperature of 38° C.and 100% relative humidity. More specifically, the barrier film can havea water vapor transmission rate of 9×10⁻⁴ g/m²·day or less, 8×10⁻⁴g/m²·day or less, 7×10⁻⁴ g/m²·day or less, 6×10⁻⁴ g/m²·day or less,5×10⁻⁴ g/m²·day or less, 4×10⁻⁴ g/m²·day or less, 3×10⁻⁴ g/m²·day orless, 2×10⁻⁴ g/m²·day or less, or 1×10⁻⁴ g/m²·day or less, as measuredunder the above conditions. The lower the water vapor transmission rateis, the better the barrier property is, and thus the lower limit of thewater vapor transmission rate is not particularly limited. In oneexample, the lower limit of the water vapor transmission rate can be0.001×10⁻⁴ g/m²·day or more, 0.005×10⁻⁴ g/m²·day or more, 0.01×10′g/m²·day or more, 0.05×10⁻⁴ g/m²·day or more, 0.1×10⁻⁴ g/m²·day or more,or 0.5×10⁻⁴ g/m²·day or more. As a representative standard for measuringthe water vapor transmission rate, ASTM F1249 or ISO15506-3, and thelike is known, where the water vapor transmission rate of the presentapplication can be measured according to the appropriate manner amongthe forgoing.

The barrier film of the present application that satisfies the lighttransmittance and barrier properties in the above-described rangecomprises a base layer and an inorganic layer. The inorganic layercomprises Si, N, and O.

The base layer can comprise, for example, glass or a polymer filmcapable of providing light transmittance.

In one example, the base layer can comprise a polymer film capable ofproviding sufficient flexibility. For example, as the base layer, apolyester film such as a polyethylene terephthalate (PET) film, apolycarbonate film, a polyethylene naphthalate film or a polyarylatefilm, a polyether film such as a polyether sulfone film, a cycloolefinpolymer film, a polyolefin film such as a polyethylene film or apolypropylene film, a cellulose resin film such as a diacetyl cellulosefilm, a triacetyl cellulose film or an acetyl cellulose butyrate film, apolyimide film, an acryl film and an epoxy resin film, and the like canbe used. In the present application, the base layer can have a singlelayer or a multilayer structure.

The thickness of the base layer is not particularly limited. Forexample, the thickness of the base layer can be about 1 μm or more, 5 μmor more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, or50 μm or more. When the thickness is satisfied, the inorganic layer canbe stably formed on the base layer. The upper limit of the base layerthickness is not particularly limited, but can be, for example, 500 μmor less, 400 μm or less, 300 μm or less, 200 μm or less, or 100 μm orless.

The inorganic layer can be formed through plasma modification of thepolysilazane composition, that is, the polysilazane layer, applied on anadherend for coating (for example, the base layer).

In the present application, the polysilazane composition means acomposition comprising polysilazane as a main component. For example,the ratio of the polysilazane in the polysilazane composition can be 55%or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% ormore, 85% or more, or 90% or more on the basis of weight. The weightratio can be, for example, 100% or less, 99% or less, 98% or less, 97%or less, 96% or less, or 95% or less.

In the present application, the polysilazane means a polymer in whichsilicon elements (Si) and nitrogen elements (N) are repeated to form abasic backbone. This polysilazane can be modified through apredetermined treatment (for example, plasma treatment) to form siliconoxide or silicon oxynitride having barrier properties. Accordingly, theinorganic layer can comprise Si, N, and O.

In one example, the polysilazane used in the present application cancomprise a unit of Formula 1 below:

In Formula 1, R¹, R² and R³ can each independently be a hydrogenelement, an alkyl group, an alkenyl group, an alkynyl group, an arylgroup, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present application, the term “alkyl group” means an alkyl grouphaving 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms,1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified.The alkyl group can be linear, branched or cyclic. In addition, thealkyl group can be optionally substituted with one or more substituents.

In the present application, the term “alkenyl group” means an alkenylgroup having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbonatoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwisespecified. The alkenyl group can be linear, branched or cyclic and canoptionally be substituted with one or more substituents.

In the present application, the term “alkynyl group” means an alkynylgroup having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbonatoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwisespecified. The alkynyl group can be linear, branched or cyclic and canoptionally be substituted with one or more substituents.

In the present application, the term “aryl group” means a monovalentresidue derived from a compound comprising a structure in which abenzene ring or two or more benzene rings are linked, or condensed orbonded while sharing one or two or more carbon elements, or a derivatethereof, unless otherwise specified. In this specification, the range ofthe aryl group can also include a so-called aralkyl group or anarylalkyl group, and the like as well as a functional group usuallyreferred to as an aryl group. The aryl group can be, for example, anaryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18carbon atoms, or 6 to 12 carbon atoms. As the aryl group, a phenylgroup, a dichlorophenyl group, a chlorophenyl group, a phenylethylgroup, a phenylpropyl group, a benzyl group, a tolyl group, a xylylgroup or a naphthyl group, and the like can be exemplified.

In the present application, the term “alkoxy group” means an alkoxygroup having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbonatoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwisespecified. The alkoxy group can be linear, branched or cyclic. Inaddition, the alkoxy group can be optionally substituted with one ormore substituents.

If the unit of Formula 1 above is included, the specific kind of thepolysilazane is not particularly limited.

In one example, the polysilazane can be polysilazane including the unitof Formula 1 in which all of R¹ to R³ are hydrogen elements, forexample, perhydropolysilazane.

In one example, the polysilazane layer composition can be prepared, forexample, by dissolving polysilazane in an appropriate organic solvent.For example, the polysilazane can be a commercially available product ina state dissolved in an organic solvent. Such a commercially availableproduct can include, for example, AQUAMICA (registered trademark)NN120-10, NN120-20, NAX120-10, NAX120-20, NN110, NN310, NN320, NL110A,NL120A, NL150A, NP110, NP140, or SP140, and the like, manufactured by AZElectronic Materials Kabushiki Kaisha (or Merck), but is not limitedthereto.

In another example, the polysilazane layer composition can be acomposition diluted to a predetermined concentration. The dilutedconcentration is not particularly limited, and for example, the weightratio of total solid content can range from 1 to 95%. In one example,the composition can have a weight ratio of total solid content of 1 to10% or less.

In the present application, the layer formed from the polysilazane, thatis, the inorganic layer, has enough durability and compactness capableof satisfying the water vapor transmission rate. In the presentapplication, the compactness can be expressed through an etching rate.For example, the inorganic layer can have an etching rate satisfying apredetermined value with respect to a reference condition. In thepresent application, the term “etching rate” means a value obtained bydividing an etched thickness (unit: nm) by an etching progress time(unit: second) on the assumption that etching is performed under thesame conditions as the reference conditions described below. The etchingfor measuring the etching rate is so-called dry etching, which is theetching using a plasma state of reactive gas. Ar is used as the reactivegas.

Regarding the etching rate of the inorganic layer, the inventors of thepresent application have confirmed that even if a similar inorganiclayer is formed from the polysilazane to include Si, N and O, so thatits constituent elements are similar, the degree of firmness orcompactness in the layer can vary depending on the contents of elementsforming the inorganic layer in the thickness direction of the inorganiclayer, the change in distribution tendency, and/or the conditions forforming the inorganic layer, and consequently, the etching rate withrespect to the reference condition can also vary. Specifically, in theprior art related to the barrier film, the type of the elements in theinorganic layer or the contents of the elements expressed as numericalvalues have been mainly considered as an important factor fordetermining the barrier properties, but the compactness of the inorganiclayer can vary depending on the contents of the elements forming theinorganic layer, the change in distribution tendency, and/or theconditions for forming the inorganic layer, and consequently, the watervapor transmission rate of the barrier film can be significantlyimproved.

Specifically, the inorganic layer can satisfy an etching rate of 0.17nm/s or less for a reference condition, that is, an Ar ion etchingcondition to etch Ta₂O₅ (film) at a rate of 0.09 nm/s or less. Theetching rate can indicate the degree of compactness in the inorganiclayer. That is, the inorganic layer having the etching rate can beconsidered to have a more dense structure than the inorganic layer thatdoes not satisfy the etching rate, for example, as in the case where theetching rate is 0.19 nm/s. For example, the inorganic layer can have anetching rate of 0.165 nm/s or less, 0.160 nm/s or less, 0.155 nm/s orless, 0.150 nm/s or less, 0.145 nm/s or less, 0.140 nm/s or less, 0.135nm/s or less, 0.130 nm/s or less, 0.125 nm/s or less, or 0.120 nm/s orless for the above condition. When the etching rate range is satisfied,it can be regarded as being sufficiently dense, and thus the lower limitof the etching rate is not particularly limited, but can be, forexample, 0.05 nm/s or more, or 0.10 nm/s or more.

The inorganic layer comprises a first region and a second region. In thepresent application, the first region is in a position that is closer tothe base layer than the second region.

In the present application, the first region and the second regionconstituting one inorganic layer have different elemental contents(atomic %) of Si, N, and O from each other as analyzed or measured byXPS (X-ray photoelectron spectroscopy) in the thickness direction. Thatis, the first region and the second region can be distinguished due tothe difference in the elemental content distribution of Si, N, and O.For example, the elemental content of each region can be analyzedaccording to the etching depth in the thickness direction of theinorganic layer, where in the case that a flat section is observed or inthe case that a section is observed, in which the magnitude tendency inthe content of each element is common, the median or average value ofthe respective elemental contents in the corresponding section can beseen as the elemental content (range) in the region, because the degreeof change in the content of each element with the depth is relativelysmall. Then, the elemental content at the interface between the firstregion and the second region can be changed continuously or stepwise inrelation to the distinction of the regions according to the elementalcontents, and as a result of these content changes, it is sufficient todistinguish the first region and the second region as long as the regionsatisfying the elemental content ratio defined by each region isobserved, and the interface between the first region and the secondregion does not necessarily need to be clearly distinguished. Thisdistinction can be clearly made by those skilled in the art through anelemental content distribution graph according to the etching depthidentified using XPS.

The first region and the second region can have the compactness asdescribed above. Specifically, the first region and/or the second regioncan each be a region where the etching rate measured under the Ar ionetching condition etching Ta₂O₅ at a rate of 0.09 nm/s satisfies 0.17nm/s or less. For example, the first region and/or the second region cansatisfy an etching rate of 0.165 nm/s or less, 0.160 nm/s or less, 0.155nm/s or less, 0.150 nm/s or less, 0.145 nm/s or less, 0.140 nm/s orless, 0.135 nm/s or less, 0.130 nm/s or less, 0.125 nm/s or less, or0.120 nm/s or less for the reference condition. The lower limit of theetching rate of the first region and/or the second region is notparticularly limited, but can be, for example, 0.05 nm/s or more or 0.10nm/s or more.

In the present application, the second region is a high nitrogenconcentration region in the inorganic layer. That is, the second regioncan be a region having a higher nitrogen content than that of the firstregion. The inventors of the present application have confirmed that thethicker the second region, which is the high nitrogen concentrationregion, the better the barrier properties (for example: water vaportransmission rate), on the assumption that the compactness of theinorganic layer identified through the etching rate is secured, like theetching rate for the reference condition is 0.17 nm/s or less. Thisresult is confirmed through the following example.

In one example, the thickness of the second region can have a thicknessof 10% or more, relative to the thickness of the entire inorganic layer.For example, the thickness of the second region can be 15% or more, 20%or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% ormore, 50% or more, 55% or more, 60% or more, 65% or more, or 70% ormore, based on the thickness of the entire inorganic layer. For example,when the thickness of the inorganic layer is 150 nm, the thickness ofthe second region can be 15 nm or more, 16 nm or more, 17 nm or more, 19nm or more, or 20 nm or more. The upper limit of the thickness of thesecond region is not particularly limited, which can be, for example,80% or less, 70% or less, 60% or less, or 50% or less, relative to thethickness of the entire inorganic layer.

In one example, the first region can be a region satisfying therelationship O content>Si content>N content. That is, the first regionmeans a region that satisfies such elemental contents.

In the present application, the content of the element is a value at thetime of regarding the sum of the contents of Si, O and N, and optionallythe content of impurities (for example: C) that can be measured in eachlayer or region as 100 in total. Unless specifically stated otherwise,the content of C is a value excluding the contents of Si, O and N, andthus it can be omitted.

Specifically, in the first region, the O content can be in a range of 50to 65 atomic %, the Si content can be in a range of 35 to 45 atomic %,and the N content can be in a range of 1 to 15 atomic %. It is believedthat such elemental contents can secure the compactness of the inorganiclayer expressed by the above-described etching rate, and can improve themoisture barrier properties of the barrier film.

In one example, the first region can satisfy a ratio (a/b) of the Ocontent (a) to the Si content (b) in a range of 1.1 to 1.9. Preferably,it can be 1.2 or more, 1.3 or more, or 1.4 or more. In the first regionwhere the contents of Si, N and O satisfy the above ranges, when theratio (a/b) value is in the range of 1.1 to 1.9, it is believed that thecompactness of the inorganic layer represented by the above-describedetching rate can be secured and the moisture barrier properties of thebarrier film can be improved.

In one example, the thickness of the first region satisfying theelemental content ratio can be 40 nm or more. When the thickness of thefirst region satisfies the above range, the inorganic layer or the firstregion can have sufficient compactness while being stably formed and canprovide the barrier film with higher durability. For example, since thebase layer adjacent to the first region or the intermediate layerdescribed below can have predetermined roughness on its surface, thefirst region can have a minimum thickness so that the inorganic layercan be stably formed. More specifically, the thickness of the firstregion satisfying the elemental content can be, for example, 45 nm ormore, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nmor more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 95nm or more, or 100 nm or more. The upper limit of the thickness of thefirst region is not particularly limited, but can be, for example, 300nm or less, 250 nm or less, or 200 nm or less.

In one example, the second region can be a region that satisfies therelationship Si content>N content>O content. That is, the second regionmeans a region that satisfies such elemental contents. As a result ofthe experimental confirmation, the case where the second regionsatisfied the relationship Si content>N content>O content could moreincrease the compactness of the inorganic layer and better adjusted thebarrier properties of the film than the case where it had Si content>Ocontent>N content.

Specifically, in the second region, the Si content can be in a range of45 to 60 atomic %, the N content can be in a range of 20 to 35 atomic %,and the O content can be in a range of 10 to 30 atomic %. Such elementalcontents are considered to be advantageous in ensuring the compactnessof the inorganic layer expressed by the above-described etching rate.

In one example, the thickness of the second region satisfying theelemental content ratio can be 10 nm or more, 20 nm or more, 30 nm ormore, 40 nm or more, or 50 nm or more. The upper limit thereof is notparticularly limited, but can be, for example, about 250 nm or less orabout 200 nm or less. As confirmed in the following example, thethickness of the second region, which is a high nitrogen concentrationregion, seems to have an effect on improving the barrier properties ofthe film, and when the thickness range is satisfied, the barrier filmcan also be formed to a thin thickness of an appropriate level andsimultaneously excellent barrier properties to the thickness can beprovided. More specifically, the thickness of the second regionsatisfying the elemental content can be, for example, 190 nm or less,185 nm or less, 180 nm or less, 175 nm or less, 170 nm or less, 165 nmor less, 160 nm or less, 155 nm or less, 150 nm or less, 145 nm or less,140 nm or less, or 135 nm or less.

In one example, the difference (d) between the maximum value of thesecond region Si content and the maximum value of the first region Ocontent can be 15 atomic % or less. In each region where the contents ofSi, N and O satisfy the above ranges, when the difference (d) issatisfied, it is believed that the compactness of the inorganic layerrepresented by the above-described etching rate can be ensured and themoisture barrier properties of the barrier film can be improved.

The formation of the first region and the second region can be performedthrough a plasma treatment of a composition comprising polysilazane,that is, a polysilazane layer.

In one example, the first region and the second region can be regions inthe inorganic layer formed through one plasma treatment performed on onecoated polysilazane composition, that is, one polysilazane layer. Thatis, the inorganic layer can be partitioned into the first region and thesecond region formed therein. It is believed that while the N-richsecond region is formed through the plasma treatment, it is divided intothe first region and the second region.

In another example, the first region and the second region can beadjacent regions formed through the plasma treatment on polysilazanelayers different from each other. For example, the first region can be aregion formed through the plasma treatment on a polysilazane layer (A),and the second region can be a region formed the plasma treatment on apolysilazane layer (B) applied on the inorganic layer on which the firstregion is formed. These first region and second region comprise Si, N,and O, and constitute an inorganic layer. As described above, the N-richregion is placed on the surface layer portion of the plasma-treatedpolysilazane layer through the plasma treatment, which is the same asthe case of the plasma-treated polysilazane layer (A), whereby it isbelieved that even if a separate plasma treatment is performed on thepolysilazane layer (B), a second region having the same elementalcontent distribution as that of the surface layer portion of thepolysilazane layer (A) is formed. In this case, the interfaces of therespective plasma-treated polysilazane layers (A, B) can be observed asa section where elemental content changes occur between the first regionand the second region, for example, as in FIG. 1. As confirmed inExamples 1 to 5 below, when the inorganic layer is formed in thismanner, it is possible to ensure a larger thickness of the secondregion, whereby the barrier properties can be improved while the highnitrogen concentration region in the inorganic layer increases.

In one example, a modified layer having a high content of carbon can bepresent between the inorganic layer and the base layer. The modifiedlayer can be an interface between the plasma-treated inorganic layer andthe base layer. Alternatively, the modified layer can be an interfacebetween the plasma-treated inorganic layer and an intermediate layerdescribed below. The modified layer can be a region containing morecarbon than the first region and the second region. For example, themodified layer can be a region that satisfies the relationship Ccontent>O content>Si content>N content.

Specifically, in the modified layer, the C content can be in a range of40 to 50 atomic %, the O content can be in a range of 30 to 40 atomic %,the Si content can be in a range of 15 to 30 atomic %, and the N contentcan be in a range of 1 to 5 atomic %.

The thickness of the inorganic layer having the first region and thesecond region can be, for example, 600 nm or less, or 500 nm or less.More specifically, the thickness of the inorganic layer can be 450 nm orless, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, or200 nm or less. The inorganic layer of the above-described configurationcan have sufficient barrier properties even at a thin thickness. Thelower limit of the thickness of the inorganic layer is not particularlylimited, but can be, for example, 50 nm or more.

In one example, the barrier film can further comprise an intermediatelayer. Specifically, the barrier film can sequentially comprise a baselayer, an intermediate layer, and an inorganic layer. The intermediatelayer can be formed for the purpose of improving adhesion force betweenthe inorganic layer and the base layer, controlling a dielectricconstant, and the like. The intermediate layer can be referred to as anunder coating layer (UC).

The intermediate layer can comprise at least one selected from the groupconsisting of an acrylic resin, a urethane resin, a melamine resin, analkyd resin, an epoxy resin, a siloxane polymer and/or a condensationproduct of an organosilane compound of the following Formula 2:

In Formula 2, X can be hydrogen, halogen, an alkoxy group, an acyloxygroup, an alkyl carbonyl group, an alkoxycarbonyl group, or —N(R₂)₂,where R₂ can be hydrogen or an alkyl group, R₁ can be an alkyl group, analkenyl group, an alkynyl group, an aryl group, an arylalkyl group, analkylaryl group, an arylalkenyl group, an alkenylaryl group, anarylalkynyl group, an alkynylaryl group, halogen, an amino group, anamide group, an aldehyde group, an alkylcarbonyl group, a carboxy group,a mercapto group, a cyano group, a hydroxy group, an alkoxy group, analkoxycarbonyl group, a sulfonyl group, a phosphoryl group, anacryloyloxy group, a methacryloyloxy group or an epoxy group, Q can be asingle bond, an oxygen element or —N(R₂)—, where R₂ can be a hydrogenelement or an alkyl group, and m can be a number in a range of 1 to 3.

As the organosilane, at least one selected from the group consisting ofthe compounds of Formula 2 above can be used, where if one organosilanecompound is used, crosslinking can be possible.

The organosilane can be selected, as an example, from the groupconsisting of methyl trimethoxysilane, methyl triethoxysilane, phenyltrimethoxysilane, phenyl triethoxysilane, dimethyl dimethoxysilane,dimethyl diethoxysilane, diphenyl dimethoxysilane, diphenyldiethoxysilane, phenyl dimethoxysilane, phenyl diethoxysilane, methyldimethoxysilane, methyl diethoxysilane, phenylmethyl dimethoxysilane,phenylmethyl diethoxysilane, trimethyl methoxysilane, trimethylethoxysilane, triphenyl methoxysilane, triphenyl ethoxysilane,phenyldimethyl methoxysilane, phenyldimethyl ethoxysilane,diphenylmethyl methoxysilane, diphenylmethyl ethoxysilane, dimethylethoxysilane, diphenyl methoxysilane, diphenyl ethoxysilane, 3-aminepropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane,p-aminophenylsilane, allyl trimethoxysilane,n-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl trimethoxysilane,3-glycidoxypropyldiisopropyl ethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyl diethoxysilane,3-methacryloxypropylmethyl dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, n-phenylaminopropyl trimethoxysilane, vinylmethyldiethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, and amixture thereof.

In another example, the intermediate layer can be produced bypolymerizing one or more polyfunctional acrylates. As the kind of thepolyfunctional acrylate, for example, bifunctional acrylates such as1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,neopentylglycol adipate di(meth)acrylate, hydroxypivalic acid neopentylglycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactonemodified dicyclopentenyl di(meth)acrylate, ethylene oxide modifieddi(meth)acrylate, di(meth)acryloxyethyl isocyanurate, allylatedcyclohexyl di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate,dimethylol dicyclopentane di(meth)acrylate, ethylene oxide modifiedhexahydrophthalic acid di(meth)acrylate, neopentyl glycol modifiedtrimethylpropane di(meth)acrylate, adamantane di(meth)acrylate or9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene; trifunctional acrylatessuch as trimethylolpropane tri(meth)acrylate, dipentaerythritoltri(meth)acrylate, propionic acid modified dipentaerythritoltri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxidemodified trimethylolpropane tri(meth)acrylate, trifunctional urethane(meth)acrylate or tris(meth)acryloxyethyl isocyanurate; tetrafunctionalacrylates such as diglycerin tetra(meth)acrylate or pentaerythritoltetra(meth)acrylate; pentafunctional acrylates such as propionic acidmodified dipentaerythritol penta(meth)acrylate; and hexafunctionalacrylates such as dipentaerythritol hexa(meth)acrylate, caprolactonemodified dipentaerythritol hexa(meth)acrylate or urethane (meth)acrylate(e.g. a reaction product of an isocyanate monomer and trimethylolpropanetri(meth)acrylate), and the like can be used, without being limitedthereto.

In one example, the intermediate layer can comprise a fluorine-basedcompound. For example, a fluorine-based (meth)acrylate or afluorine-based siloxane compound can be used. Although not particularlylimited, a perfluoro compound such as perfluoropolyether acrylate can beused as the fluorine-based (meth)acrylate, and an alkoxysilane compoundsubstituted with a fluorine-containing chain can be used as thefluorine-based siloxane compound.

As the epoxy resin applicable to the formation of the intermediatelayer, at least one selected from the group consisting of an alicyclicepoxy resin and an aromatic epoxy resin can be used.

As the alicyclic epoxy resin, for example, at least one selected fromthe group consisting of an alicyclic glycidyl ether type epoxy resin andan alicyclic glycidyl ester type epoxy resin can be used. Also, forexample, 3,4-epoxycyclohexyl-methyl-3,4-epoxy cyclohexane carboxylate,which is Celloxide 2021P (Daicel Co.), and derivatives thereof can beused, which are stable even at high temperatures, colorless andtransparent, and have excellent toughness, adhesion and adhesiveness forlamination. Especially, when used for coating, they have excellentsurface hardness.

As the aromatic epoxy resin, for example, at least one aromatic epoxyresin selected from the group consisting of a bisphenol A type epoxyresin, a brominated bisphenol A type epoxy resin, a bisphenol F typeepoxy resin, a bisphenol AD type epoxy resin, a fluorene-containingepoxy resin and triglycidyl isocyanurate can also be used.

The intermediate layer can be, for example, a coating layer formed by asol-gel reaction. For example, at least one selected from the groupconsisting of SiOx (where, x is an integer of 1 to 4), SiOxNy (where, xand y are each an integer of 1 to 3), Al₂O₃, TiO₂, ZrO and ITO can alsobe included in the intermediate layer.

The intermediate layer can also comprise a metal alkoxide of Formula 3below, or a condensation product thereof:

M

R₃]_(z)  Formula 3

In Formula 3, M can be any one metal selected from the group consistingof aluminum, zirconium, and titanium, R₃ can be halogen, an alkyl group,an alkoxy group, an acyloxy group, or a hydroxy group, and z can be 3 or4.

In one example, the intermediate layer can further comprise a filler.The filler can be used in consideration of, for example, adjusting therefractive index of the intermediate layer and/or adjusting themechanical strength, and the like. In one example, as the filler, atleast one selected from the group consisting of CaO, CaF₂, MgO, ZrO₂,TiO₂, SiO₂, In₂O₃, SnO₂, CeO₂, BaO, Ga₂O₃, ZnO, Sb₂O₃, NiO and Al₂O₃ canbe used.

The method of forming the intermediate layer using the above materialsis not particularly limited and known methods, for example, various dryand/or wet coating methods such as a deposition method and a sol-gelcoating method, can be used depending on the materials to be used.

The thickness of the intermediate layer is not particularly limited. Forexample, it can be 50 μm or less. Specifically, the upper limit of thethickness can be 40 μm or less, 30 μm or less, 20 μm or less, 10 μm orless, or 5 μm or less, and the lower limit can be 0.5 μm or more, or 1μm or more.

In one example, the intermediate layer can be a layer that provides aflat surface on which an inorganic layer can be formed. That is, theintermediate layer can be a planarizing layer. The planarizing layer canbe a layer that average surface roughness (Rt) of one surface oppositeto a surface facing a base layer, that is, a surface on which aninorganic layer is formed, is in a range of 15 to 45 nm. The surfaceroughness of the intermediate layer means an average value for theheight difference between the highest part and the lowest part in apredetermined region having roughness, which can be measured in the samemanner as described in the following example.

In one example, the first region of the inorganic layer can have athickness of at least twice or more relative to the average surfaceroughness (Rt) of the planarizing layer. For example, when the averagesurface roughness (Rt) of the planarizing layer is 20 nm, the thicknessof the first region can be 40 nm or more, and in another example, whenthe average surface roughness (Rt) of the planarizing layer is 30 nm,the thickness of the first region can be 60 nm or more. When theplanarizing layer and the first region satisfy the thicknessrelationship in the barrier film, the inorganic layer can be stablyformed. Then, the stably formed inorganic layer can provide an excellentwater vapor transmission rate. Although not particularly limited, ingeneral, when the planarizing layer of the composition is formed, it canbe preferable that the thickness of the first region is about 60 nm ormore, 65 nm or more, 70 nm or more, or 75 nm or more, considering thatthe surface roughness formed on one surface thereof is about 20 nm ormore, 25 nm or more or 30 nm or more. At this time, the upper limit ofthe thickness of the first region can also be, for example, in the rangeof 300 nm.

The barrier film can be produced according to a predetermined method.

For example, the method for producing a barrier film can comprise stepsof: applying a polysilazane composition on an adherend for coatingincluding a base layer; and performing a plasma treatment on thepolysilazane layer formed on the adherend for coating. The productionmethod will be described in detail as follows.

The plasma treatment is performed by generating plasma under anatmosphere containing a plasma generation gas such as Ar and injectingpositive ions in the plasma to the polysilazane layer, where the plasmacan be generated, for example, by an external electric field or anegative high voltage pulse. This plasma treatment can be performedusing a known apparatus.

The plasma treatment can be performed under the following conditions.

In one example, the plasma treatment can be performed by a method ofadjusting a distance of a plasma treatment object from an electrode. Atthis time, the plasma treatment object can mean a laminate in a statewhere a polysilazane composition is coated on an adherend for coating(for example, a base layer), or a laminate in a state where apolysilazane layer is formed through a predetermined warming (heating)state of the composition applied to the adherend for coating. Such alaminate can be referred to as a barrier film precursor. For example,upon the plasma treatment, the distance of the barrier film precursorfrom the electrode (positive and/or negative electrode) can be adjustedto 150 mm or less. It is believed that the closer the distance betweenthe precursor sample and the positive electrode is in the range thatsatisfies the above distance, plasma energy can be transferred to thebarrier film precursor while reducing the loss of plasma energy and thepossibility of polysilazane modification can be increased while thermalenergy generated upon plasma discharge is effectively transferred to theprecursor. For example, the distance can be 140 mm or less, 130 mm orless, 120 mm or less, 110 mm or less, 100 mm or less, 90 mm or less, or80 mm or less. The lower limit of the distance is not particularlylimited, but if the distance between the negative electrode and thebarrier film precursor is too close, there is a possibility of damage tothe base layer, and thus for example, the lower limit of the distancecan be 15 mm or more, or 20 mm or more.

In one example, the plasma treatment can be performed under apredetermined power density. Specifically, upon the plasma treatment,the power density per unit area of the electrode can be about 0.05 W/cm²or 0.10 W/cm² or more. In another example, the power density can beabout 0.2 W/cm² or more, about 0.3 W/cm² or more, about 0.4 W/cm² ormore, about 0.5 W/cm² or more, about 0.6 W/cm² or more, about 0.7 W/cm²or more, about 0.8 W/cm² or more, or about 0.9 W/cm² or more. Within therange that satisfies the power density, in the case of the positiveelectrode, the higher the power density, the degree of plasma treatmentcan be increased for a short time and the degree of modification of thepolysilazane due to application of a high voltage can be increased. Inthe case of the negative electrode, the excessively high power densitycan cause damage to the base layer due to a high voltage, and thusconsidering this point, the upper limit of the power density can beabout 2 W/cm² or less, 1.5 W/cm² or less, or 1.0 W/cm² or less.

In one example, in the case of having the power density, the processingenergy upon the plasma treatment, which is determined by multiplying thepower density by the processing time, can be 50 J/cm² or less.Specifically, the energy can be 45 J/cm² or less, 40 J/cm² or less, 35J/cm² or less, 30 J/cm² or less, 25 J/cm² or less, 20 J/cm² or less, andthe lower limit can be 5 J/cm² or more, 10 J/cm² or more, or 15 J/cm² ormore.

In one example, the plasma treatment can be performed under apredetermined process pressure. Specifically, the process pressure uponthe plasma treatment can be 350 mTorr or less. In the case of thepositive electrode, the lower the process pressure, the easier theaverage free path is secured, and thus the plasma treatment can beperformed without energy loss due to collision with gas molecules. Forexample, the process pressure can be 340 mTorr or less, 330 mTorr orless, 320 mTorr or less, 310 mTorr or less, 300 mTorr or less, 290 mTorror less, 280 mTorr or less, 270 mTorr or less, 260 mTorr or less, 250mTorr or less, 240 mTorr or less, 230 mTorr or less, 220 mTorr or less,210 mTorr or less, or 200 mTorr or less. On the other hand, in the caseof the negative electrode, the lower the process pressure is, the lessthe gas molecules are, and thus high voltage and power can be requiredto generate the plasma, where the high voltage and the high power cancause damage to the base layer, and for example, the lower limit can be50 mTorr or more, 60 mTorr or more, 70 mTorr or more, 80 mTorr or more,90 mTorr or more, 100 mTorr or more, 110 mTorr or more, 120 mTorr ormore, 130 mTorr or more, 140 mTorr or more, 150 mTorr or more, 160 mTorror more, 170 mTorr or more, 180 mTorr or more, or 190 mTorr or more. Thepressure can be a pressure at the beginning of the process and thepressure can be maintained within the range during the process.

In one example, the plasma treatment can be performed while adjustingthe type and flow rate of process gases. Specifically, the plasmatreatment can be performed while injecting water vapor, discharge gas(Ar) and oxygen into the processing space. When the plasma treatment isperformed under such a process gas atmosphere, it is believed that thehydrogen radicals dissociated from the water vapor in the processingspace remove hydrogen elements of the polysilazane and combine to formhydrogen (H₂), whereby the reactivity of the polysilazane can increase,and as a result, the barrier properties can be improved.

When water vapor, discharge gas and oxygen are used as process gases,the vapor pressure of water vapor in the processing space can be 5% ormore. The water vapor pressure is the percentage of the injection flowrate of the injected water vapor, relative to the total flow rate of thegases injected into the processing space, where in the case ofperforming the plasma treatment while injecting water vapor, a dischargegas and a reaction gas at flow rates of A sccm, B sccm and C sccm,respectively, the water vapor pressure can be calculated as100%×A/(A+B+C). In another example, the water vapor pressure can beabout 10% or more, about 15% or more, about 20% or more, about 25% ormore, or about 30% or more. The upper limit of the water vapor pressureis not particularly limited and can be, for example, about 90% or less,about 85% or less, about 80% or less, about 75% or less, about 70% orless, about 65% or less, about 60% or less, about 55% or less, about 50%or less, about 45% or less, about 40% or less, or about 35% or less.

In order to maintain the water vapor pressure to the above level, theplasma treatment can be performed while introducing water vapor having apredetermined flow rate or more into the space. For example, themodification treatment can be performed while injecting the water vaporat a flow rate of 50 sccm or more in the processing space. In anotherexample, the injection flow rate of the water vapor can be 60 sccm ormore, 70 sccm or more, 80 sccm or more, 90 sccm or more, 100 sccm ormore, 110 sccm or more, or 120 sccm or more. The upper limit of theinjection flow rate is not particularly limited, and for example, theinjection flow rate can be about 500 sccm or less, 400 sccm or less, 300sccm or less, 200 sccm or less, or about 150 sccm or less.

The hydrogen partial pressure in the processing space can be controlledby maintaining the water vapor pressure as above.

When the type and vapor pressure of the process gas are adjusted asabove, dehydrogenation of the polysilazane layer can be performed byhydrogen radicals generated from water vapor, thereby adjusting thepartial pressure of hydrogen in the processing space. For example, thepartial pressure of hydrogen (H2) in the processing space can range fromabout 2.00×10⁻⁵ Pa to 1.00×10⁻⁴ Pa.

In one example, with respect to plasma processing conditions, theinjection flow rates of discharge gas and water vapor can be adjusted.Specifically, the ratio (H/N) of the injection flow rate (H) of thewater vapor to the injection flow rate (N) of the discharge gas for theprocessing space can be maintained at 0.4 or more. In another example,the ratio (H/N) can be maintained at about 0.45 or more or about 0.5 ormore. The upper limit of the ratio (H/N) is not particularly limited andcan be, for example, about 5 or less, about 4 or less, about 3 or less,about 2 or less, about 1 or less, or about 0.9 or less. Under such arange, the modification treatment can be effectively performed.

In one example, with respect to plasma processing conditions, theinjection flow rates of water vapor and oxygen can be adjusted.Specifically, the ratio (H/O) of the injection flow rate (H) of thewater vapor to the injection flow rate (O) of the oxygen gas for theprocessing space can be 0.4 or more. In another example, the ratio (H/O)can be maintained at about 0.45 or more, or about 0.5 or more. The upperlimit of the ratio (H/O) is not particularly limited and can be, forexample, about 5 or less, about 4 or less, about 3 or less, about 2 orless, about 1 or less, or about 0.9 or less. Under such a range, themodification treatment can be effectively performed.

The temperature at which the plasma treatment is performed is notparticularly limited, but if the temperature increases, the reaction forforming the barrier layer can be made smoother, whereby it can beappropriate to perform the treatment above room temperature. Forexample, the process temperature during the modification treatment canbe 30° C. or higher, 40° C. or higher, 50° C. or higher, 60° C. orhigher, 70° C. or higher, or 80° C. or higher. In another example, theprocess temperature can be about 85° C. or higher, about 90° C. orhigher, about 95° C. or higher, about 100° C. or higher, about 105° C.or higher, or about 110° C. or higher. The process temperature can bemaintained at about 200° C. or lower, about 190° C. or lower, about 180°C. or lower, about 170° C. or lower, about 160° C. or lower, about 150°C. or lower, about 140° C. or lower, about 130° C. or lower, or about120° C. or lower.

The plasma treatment time can be appropriately adjusted at a level thatdoes not hinder the barrier properties of the film. For example, theplasma treatment can be performed for a time of about 10 seconds to 10minutes.

The polysilazane layer formed on the adherend for coating can bemodified through the plasma treatment under the above conditions,whereby the properties of the barrier film described above can beimparted. For example, upon the formation of the inorganic layer, thepolysilazane undergoes a dehydrogenation crosslinking reaction or asilica formation reaction, where it is believed that if the first regionadjacent to the base layer in the inorganic layer or the intermediatelayer described below is formed, residual moisture or oxygen is suppliedfrom the organic portion derived from the base layer or the intermediatelayer, so that silica formation occurs predominantly. In addition, uponthe formation of the second region, the supply of residual moisture,oxygen, etc. derived from the base layer or the intermediate layer islimited by the first region already formed, so that it is believed thatthe nitrogen content increases as the dehydrogenation crosslinkingreaction progresses considerably. Then, it is believed that thecompactness is given to the inorganic layer having such elementalcontents (distribution).

In one example, the method for producing a barrier film can furthercomprise a heating step for the film precursor before performing theplasma treatment. The heating can be performed, for example, in therange of 40 to 150° C. for several minutes to several hours. After thesolvent is evaporated through the heating, the plasma treatment can beperformed.

The barrier film of the present application formed by such a manner hasexcellent barrier properties, so that it can be used in variousapplications such as packaging materials of foods, drugs or the like,members for FPDs (flat panel displays) such as LCDs (liquid crystaldisplays) or solar cells, substrates for electronic papers or OLEDs(organic light emitting diodes) or sealing films. Particularly, thebarrier film formed in the above-described manner has excellent opticalperformances such as transparency and thus can be effectively used inoptical devices such as various display devices or lighting devices.

When it is used for such a use, the lamination order of the barrier filmand the optical device is not particularly limited.

For example, the barrier film can be positioned such that its secondregion is adjacent to an object to be protected, i.e., a configurationvulnerable to moisture. Specifically, when the barrier film is attachedto an OLED element, the lamination order can be the base layer, thefirst region, the second region, and the OLED element. At this time, thesecond region can be formed directly on the OLED or be adjacent to theOLED via another layer configuration.

In another example, the first region can be located to be adjacent to anobject to be protected, i.e., a configuration vulnerable to moisture.Specifically, when the barrier film is attached to the OLED element, thelamination order can be the OLED, the first region, and the secondregion. At this time, the first region can be formed directly on theOLED or be adjacent to the OLED via another layer configuration.

In another example of the present application, the present applicationrelates to an electrical or electronic element. These elements cancomprise a barrier film having the same configuration or properties asdescribed above.

In yet another example of the present application, the presentapplication relates to a method for producing a barrier film. The methodcan comprise steps of applying a polysilazane composition on a baselayer and subjecting it to a plasma treatment.

Specific features and configurations of the base layer and thepolysilazane composition are as described above.

In addition, the above-described contents can also be equally applied tothe plasma treatment method for forming an inorganic layer.

Advantageous Effects

According to one example of the present application, a barrier filmhaving excellent barrier properties and light transmittance can beprovided.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows the XPS analysis results for the inorganic layer of Example1.

FIG. 2 shows the XPS analysis results for the inorganic layer of Example4.

FIG. 3 shows the XPS analysis results for the inorganic layer ofComparative Example 1.

FIG. 4 is a view obtained by TEM analyzing the cross section of thebarrier film of Example 4.

EXAMPLES

Hereinafter, the barrier film of the present application will bedescribed through examples according to the present application andcomparative examples, but the scope of the present application is notlimited by the following examples.

Measuring Method

-   -   Water vapor transmission rate: Using MOCON Aquatron II, the        water vapor transmission rate of the produced barrier film was        measured at 38° C. and 100% relative humidity conditions.    -   Etching rate and elemental content analysis: The element        distribution analysis in the depth (thickness) direction from        the surface of the inorganic material layer to the base material        direction was performed while gradually removing the inorganic        layer using Ar ions. As the etching conditions, an Ar ion        setting with an etching rate of 0.09 nm/s for Ta₂O₅ as the        reference material was used. In addition, the elemental contents        of the inorganic layer were analyzed using XPS (X-ray        photoelectron spectroscopy) (C can be detected as an impurity        derived from the base material).

EXAMPLES AND COMPARATIVE EXAMPLES

The thickness, etching rate and water vapor transmission rate of thebarrier film produced as described below were measured, and the resultswere described in Table 1.

Example 1

A planarizing layer having a thickness of 1 μm was laminated on a PET(poly(ethylene terephthalate)) film (a product from Teijin Co., Ltd.)having a thickness of about 50 μm, and an inorganic material layer wasformed on the planarizing layer. The specific process is as follows.

-   -   Formation of planarizing layer: A composition comprising 2        ratios by weight of a photocuring initiator to a mixture of        fluorine-based acrylate HR6060:PETA (pentaerythritol        triacrylate):DPHA (dipentaerythritol hexaacrylate) in a content        (weight) ratio of 80:10:10 was diluted in PGME (propylene glycol        methyl ether) to 25% to prepare a coating liquid for a        planarizing layer. The coating liquid was applied onto a PET        film as a base material using a Mayer bar, and dried at 100° C.        for 5 minutes. Subsequently, the coating layer was irradiated        with ultraviolet rays at 0.6 J/cm² by a mercury lamp, and cured        to form a planarizing layer.

Formation of inorganic coating layer (1): Polysilazane was diluted to3.7% with Merck's NL grade dibutylether, coated on the planarizing layerusing a Mayer bar, and then dried at 100° C. for 5 minutes. A plasmatreatment was performed on the polysilazane coating layer under thefollowing conditions, and an inorganic coating layer was formed.Regarding the concentration of the diluted polysilazane, % means theweight ratio of the total solid content.

-   -   Pressure 250 mTorr (flow rate on the basis of sccm atmosphere of        Ar:O₂:H₂O=1.5:1:1)    -   Distance between polysilazane coated surface and electrode 25 mm    -   Power density: supply of DC power 0.8 W/cm² for 25 seconds

Example 2

On the inorganic coating layer (1) manufactured in Example 1, apolysilazane layer was further formed by using a coating liquid having asilazane concentration of 1%, and the plasma treatment was performedunder the same conditions as in Example 1 to further laminate aninorganic coating layer (2).

Example 3

On the inorganic coating layer (1) manufactured in Example 1, apolysilazane layer was further formed by using a coating liquid having asilazane concentration of 2.4%, and the plasma treatment was performedunder the same conditions as in Example 1 to further laminate aninorganic coating layer (2-1).

Example 4

On the inorganic coating layer (1) manufactured in Example 1, apolysilazane layer was further formed by using a coating liquid having asilazane concentration of 3.7%, and the plasma treatment was performedunder the same conditions as in Example 1 to further laminate aninorganic coating layer (2-2).

Example 5

A barrier film comprising a base layer/a planarizing layer/an inorganiccoating layer (1-1) was produced in the same method as in Example 1,except that upon producing the inorganic layer, a coating liquid havinga silazane concentration of 2.4% was applied on the planarizing layerand the plasma treatment conditions were changed as follows. Thereafter,a coating liquid having a silazane concentration of 2.4% was appliedonto the inorganic coating layer (1-1), and the plasma treatment wasperformed under the following conditions to produce a barrier filmcomprising the base layer/the planarizing layer/the inorganic coatinglayer (1-1)/the inorganic coating layer (2-3).

-   -   Pressure 150 mTorr (flow rate on the basis of sccm atmosphere of        Ar:O₂:H₂O=1.5:1:1)    -   Distance between polysilazane coated surface and electrode 40 mm    -   Power density: supply of DC power 0.45 W/cm² for 45 seconds

Comparative Example 1

A barrier film was produced in the same manner as in Example 1, exceptthat the polysilazane solution diluted to 4.5% was used and the plasmaconditions were changed as follows.

-   -   Pressure 100 mTorr (flow rate on the basis of sccm atmosphere of        Ar:O₂=1:1)    -   Distance between polysilazane coated surface and electrode 10 mm    -   Power density: supply of DC power 0.3 W/cm² for 65 seconds

Comparative Example 2

A barrier film was produced in the same method as in Comparative Example1, except that the polysilazane solution diluted to 4.9% was used andthe distance from the electrode was 175 mm.

TABLE 1 Inorganic layer (first region + Water vapor second region)Second region transmission Thickness Etching time Etching rate EtchingThickness rate (nm) (s) (nm/s) time (s) (nm) (×10⁻⁴ g/m² · day) Example1 150 925 0.162 105 17 7.0 2 185 1,180 0.157 380 57 2.3 3 215 1,3100.164 540 86 <0.5 4 250 1,600 0.156 800 125 <0.5 5 165 1,000 0.165 630100 <0.5 Comparative 1 180 700 0.257 180 46 23.9 Example 2 200 760 0.263130 34 12.0 * The thickness of the second region was obtained bymultiplying ‘the etching time for the second region distinguishedthrough the XPS analyses’ and ‘the etching rate for the inorganiclayer.’

As in Table 1, it can be seen that Examples comprising the inorganiclayer satisfying an etching rate of 0.17 nm/s or less have very lowwater vapor transmission rates relative to Comparative Examples which donot satisfy the etching rate. In particular, in can be confirmed that inthe case of Example 1 of the present application, the thickness of theinorganic layer is thinner than those of Comparative Examples, but theexcellent barrier properties can be ensured. This means that theinorganic layers of the barrier films in Examples are denser than theinorganic layers of the barrier films in Comparative Examples. Inaddition, the 4.9% silazane solution was used when forming the barrierfilm of Comparative Example 2 and the 2.4% silazane solution was usedtwice when forming the barrier film of Example 5, whereby theconcentrations of the silazane solutions were almost similar (theconcentration of Comparative Example was higher), but it can be seenthat the difference in water vapor transmission rate occurred. Thissuggests that the compactness of the film is not due to theconcentration of the coating solution.

Under the premise that they have similar compactness degrees, it iscommon that if the thickness of the layer increases, the barrierproperties to gas or moisture increase (see water vapor transmissionrates of Comparative Examples 1 and 2). In this regard, comparingExample 2 with Example 5, it can be seen that the water vaportransmission rate of Example 5 having a lower thickness is lower. Thisis because the thickness of the second region, which is a high nitrogenconcentration region, is larger in the film of Example 5. This is alsoconfirmed when comparing the thicknesses of the second regions ofExamples 1 to 5. That is, like the etching rate for the referenceconditions is 0.17 nm/s or less, it can be confirmed that under thepremise that the compactness of the inorganic layer identified throughthe etching rate is ensured, the thicker the second region, which is ahigh nitrogen concentration region, the water vapor transmission rate isimproved (reduced).

On the other hand, the second regions of the films in Examples 3 and 5have been formed equally from the 2.4% silazane solution, but the secondregions have different thicknesses. That is, by appropriately adjustingthe above-mentioned conditions upon the plasma treatment, the thicknessof the second region, which is a high nitrogen concentration region, canbe increased and the barrier properties of the barrier film can be moreimproved.

1. A barrier film comprising: a base layer; and an inorganic layerincluding a first region and a second region, which have differentelemental contents (atomic %) of Si, N, and O from each other asmeasured by XPS, and having a compactness expressed through an etchingrate of 0.17 nm/s or less in the thickness direction for an Ar ionetching condition to etch Ta₂O₅ at a rate of 0.09 nm/s, wherein thesecond region has a higher elemental content of N than that of the firstregion, and the second region has a thickness of 10% or more relative tothe total thickness of the inorganic layer.
 2. The barrier filmaccording to claim 1 having a water vapor transmission rate measured ata temperature of 38° C. and 100% relative humidity of 10×10⁻⁴ g/m²·dayor less.
 3. The barrier film according to claim 1, wherein the firstregion is in a position closer to the base layer than the second region.4. The barrier film according to claim 1, wherein the first regionsatisfies the relationship: O content>Si content>N content.
 5. Thebarrier film according to claim 4, wherein the O content of the firstregion is in a range of 50 to 65 atomic %, the Si content of the firstregion is in a range of 35 to 45 atomic %, and the N content of thefirst region is in a range of 1 to 15 atomic %.
 6. The barrier filmaccording to claim 5, wherein the first region has a ratio (a/b) of theO content (a) to the Si content (b) in a range of 1.1 to 1.9.
 7. Thebarrier film according to claim 5, wherein the second region satisfiesthe relationship: Si content>N content>O content.
 8. The barrier filmaccording to claim 7, wherein the Si content of the second region is ina range of 45 to 60 atomic %, the N content of the second region is in arange of 20 to 35 atomic %, and the O content of the second region is ina range of 10 to 30 atomic %.
 9. The barrier film according to claim 8,wherein the difference between the highest value of the Si content inthe second region and the highest value of the O content in the firstregion is 15 atomic % or less.
 10. The barrier film according to claim1, wherein the inorganic layer is obtained by plasma-treatingpolysilazane having a unit of Formula 1 below:

wherein, R¹, R² and R³ are each independently a hydrogen atom, an alkylgroup, an alkenyl group, an alkynyl group, an aryl group, an alkylsilylgroup, an alkylamino group or an alkoxy group.
 11. An electrical orelectronic element comprising the barrier film according to claim 1.